CN103534383B - Film forming device - Google Patents
Film forming device Download PDFInfo
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- CN103534383B CN103534383B CN201180069697.2A CN201180069697A CN103534383B CN 103534383 B CN103534383 B CN 103534383B CN 201180069697 A CN201180069697 A CN 201180069697A CN 103534383 B CN103534383 B CN 103534383B
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- substrate
- film forming
- forming device
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- film
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- 239000000758 substrate Substances 0.000 claims abstract description 87
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000010408 film Substances 0.000 description 76
- 239000007789 gas Substances 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 239000010409 thin film Substances 0.000 description 15
- 238000002161 passivation Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000003079 width control Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
- C23C16/509—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using internal electrodes
- C23C16/5096—Flat-bed apparatus
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45563—Gas nozzles
- C23C16/45565—Shower nozzles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45563—Gas nozzles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
- C23C16/509—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using internal electrodes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/515—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using pulsed discharges
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The present invention proposes a kind of film forming device, forms passivating film, and includes: chamber, be imported into the reacting gas of the unstrpped gas comprising passivating film on substrate；Substrate base, is configured in chamber, and mounting substrate；Electrode, is configured in chamber, in substrate base relative with substrate to face form groove；And alternating current power supply, while making stopping for the cycle giving to fix of the alternating electromotive force more than or equal to 50kHz and the frequency less than or equal to 450kHz, while by the supply of this alternating electromotive force between substrate base and electrode, and excite, at the upper surface of substrate, the plasma comprising unstrpped gas.
Description
Technical field
The present invention relates to one excites plasma (plasma) to carry out the thin film formation of film forming process
Device.
Background technology
In the manufacturing process of semiconductor element, easily carry out high-precision technique (process) because having
The advantage controlled, so use in film formation process, etching procedure, ashing (ashing) operation etc.
Plasma processing apparatus.Such as, as plasma processing apparatus, it is known to plasma chemistry
Vapour deposition (chemical vapor deposition, CVD) device.
In plasma CVD equipment, utilize RF power etc. by plasmarized for unstrpped gas, and profit
On substrate, thin film is formed with chemical reaction.And, in order to improve film forming efficiency, and propose favourable
The plasma CVD equipment that discharges with hollow cathode (hollow cathode) (for example, referring to
Patent documentation 1).
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2004-296526 publication
Summary of the invention
[inventing problem to be solved]
In the passivating films such as the antireflection film of crystalline silicon solar cell, generally use refractive index be 1.9～
2.4, thickness is the silicon nitride film etc. of 70nm～about 100nm.In the case of forming this kind of thin film,
About the frequency of the alternating current power supply of plasma CVD equipment, if used less than or equal to 1MHz's
Low frequency, then the passivation effect of inside of the surface of crystal silicon film and the substrate that forms crystal silicon film carries
Height, the conversion efficiency of solar cell improves.But, if using the low frequency less than or equal to 1MHz
Rate, then plasma density during film-forming process reduces, and film forming efficiency reduces.
On the other hand, use hollow cathode discharge plasma CVD equipment in, use more than or
The alternating current power supply of the frequency equal to 1MHz.Such as forming thin film transistor (TFT) (Thin Film
Transistor, TFT) thin film silicon fiml in the case of, even with more than or equal to 1MHz's
Frequency also will not occur problem especially.But, the antireflection film of crystalline silicon solar cell is being entered
In the case of row film forming etc., there is following problems: if more than or frequency equal to 1MHz
Alternating current power supply, then the surface of crystal silicon film and the passivation effect within substrate decline, turning of solar cell
Change efficiency to reduce.
In view of described problem, the decline that it is an object of the invention to provide formation passivation effect is suppressed
Thin film and the high film forming device of film forming efficiency.
[for solving the means of problem]
A form according to the present invention, it is provided that a kind of film forming device forming passivating film on substrate,
Comprising: (a) chamber, it is imported into the reacting gas of the unstrpped gas comprising passivating film, (b) substrate
Base plate, is configured in chamber, and mounting substrate, (c) electrode, is configured in chamber, in substrate base
On plate relative with substrate to face form groove, (d) alternating current power supply, make more than or equal to 50
Stopping for the cycle giving to fix of the alternating electromotive force of kHz and the frequency less than or equal to 450kHz, one
While by the supply of this alternating electromotive force between substrate base and electrode, and excite at the upper surface of substrate and comprise
The plasma of unstrpped gas.
(effect of invention)
According to the present invention, it is possible to provide form the thin film that suppressed of decline and the film forming efficiency of passivation effect
High film forming device.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the composition of the film forming device representing embodiments of the present invention.
Fig. 2 is the surface of the electrode representing the film forming device being formed at embodiments of the present invention
The schematic diagram of the example of groove.
Fig. 3 is the relation of frequency and the number of ions colliding substrate surface representing supplied electric power
Curve chart.
Fig. 4 is the curve chart representing substrate temperature with the relation of conversion efficiency.
Fig. 5 be the thin film that carries out of the film forming device representing and utilizing embodiments of the present invention formed with
The form of the comparison that the thin film of comparative example is formed.
Fig. 6 is the schematic diagram of the composition of the film forming device of other embodiments representing the present invention.
Fig. 7 is the schematic diagram of the composition of the film forming device of other embodiments representing the present invention.
[explanation of symbol]
10: film forming device 11: chamber
12: substrate base 13: electrode
14: alternating current power supply 15: gas supply mechanism
16: gas-venting mechanism 17: heater
100: substrate 110: passivating film
120: reacting gas 130: face
131: squit hole 132: groove
141: matching box
Detailed description of the invention
Referring to the drawings, embodiments of the present invention are illustrated.In the record of following accompanying drawing, right
Same or similar part encloses same or similar symbol.Wherein, it is schematic for should noticing accompanying drawing
Figure.And, embodiment shown below has illustrated in order to by the technological thought materialization of the present invention
Device or method, in embodiments of the present invention, the structure of constituent part, configuration etc. not specifically for
The description below.Embodiments of the present invention can add various change in the claims.
The film forming device 10 of embodiments of the present invention is to form passivating film 110 on the substrate 100
Film forming device.As it is shown in figure 1, film forming device 10 includes: chamber 11, it is imported into bag
The reacting gas 120 of the unstrpped gas containing passivating film 110；Substrate base 12, is configured in chamber 11,
And mounting substrate 100；Electrode 13, is configured in chamber 11, in substrate base 12 and substrate
100 relatively to face on, configure the peristome of the multiple squit holes 131 supplying reacting gas 120 to pass through
And it is formed at the groove 132 of the surrounding of this peristome；And alternating current power supply 14, make to be more than or equal to
Stopping for the cycle giving to fix of the alternating electromotive force of 50kHz and the frequency less than or equal to 450kHz,
While by the supply of this alternating electromotive force between substrate base 12 and electrode 13, and upper at substrate 100
Surface excitation comprises the plasma of unstrpped gas.
Reacting gas 120 is directed in chamber 11 by gas supply mechanism 15.And, utilize gas
Body output mechanism 16 reduces pressure in chamber 11.By the pressure tune of the reacting gas in chamber 11
After the whole air pressure for regulation, via matching box (matching box) 141, by alternating current power supply 14
By the alternating electromotive force supply of regulation between set substrate base 12 and electrode 13.Thus, chamber
The reacting gas 120 comprising unstrpped gas in room 11 is in plasma.By by sudden and violent for substrate 100
It is exposed in formed plasma, and forms desired thin film on the surface exposed of substrate 100.
As it is shown in figure 1, electrode 13 relative with substrate 100 to surface configuration squit hole 131
Peristome and groove 132, electrode 13 plays as the hollow cathode electrode producing hollow cathode discharge
Function.It is, in being formed at the groove 132 on surface of electrode 13, cause hollow cathode effect
The inclosure of electronics, stably generates high-density plasma with the form that supplies from groove 132.As a result,
Unstrpped gas is decomposed efficiently, thus at a high speed, large area and formed blunt the most on the substrate 100
Change film 110.
Fig. 2 is expressed as follows example: electrode 13 relative with substrate 100 to face 130 on, along
The orientation of a line squit hole 131 and around squit hole 131, be continuously formed groove 132.As long as
It is configured at around the peristome of squit hole 131, then the layout (layout) of groove 132 can use
Various compositions.Such as, additionally it is possible to configure the side of the peristome of squit hole 131 with the point of intersection at grid
Formula, clathrate landform grooving 132.
Generally, utilizing hollow cathode discharge in the case of exciting plasma, supplying between electrode
The frequency of alternating electromotive force be more than or equal to 1MHz.Therefore, using 50kHz's～450kHz
In the film forming device 10 of the alternating electromotive force of frequency, in order to be stably formed in chamber 11 etc. from
Daughter, and make the supply of alternating electromotive force stop with the fixing cycle.
It is, alternating current power supply 14 Pulse Width Control is to the alternating current between substrate base 12 and electrode 13
The supply of power, and periodically turn on/off the supply of alternating electromotive force.Such as, alternating electromotive force will be supplied
Turn-on time be set to 600 microseconds, the turn-off time of the supply stopping alternating electromotive force being set to 50 microseconds,
And with turn-on time and alternately repeated mode turn-off time, between substrate base 12 and electrode 13
Supply alternating electromotive force.It addition, the time that will turn on is set as 300 microseconds～1500 microseconds, disconnect
Time is set as 25 microseconds～50 microseconds.If the time of will be switched off is set to long, then power effect
Rate reduces, and is preferably set to 50 microseconds the longest turn-off time.Generally, at alternating electromotive force
Frequency be more than or equal to 1MHz in the case of, the supply of alternating electromotive force need not be disconnected.
The alternating electromotive force being fed in film forming device 10 between substrate base 12 and electrode 13
Frequency is set to 50kHz～450kHz, when being to be formed with plasma in chamber 11
Make to collide the increasing number of the ion of substrate 100.Thus, as described below, it is possible to increase
The surface of substrate 100 and the passivation effect of inside, and improve the conversion efficiency of crystalline silicon solar cell
Deng.
Such as polycrystalline silicon substrate is used in the substrate of crystalline silicon solar cell.In polycrystalline silicon substrate,
The crystal boundary of polysilicon becomes defect.This defect is supplied by carrier, thus conversion efficiency reduces.But,
By making hydrogen (H) ion etc. collide with substrate 100, and available H ion makes knot in polysilicon
Brilliant dangling bonds (dangling bond) terminates.Thus, defect the carrier caused supply minimizing,
Thus passivation effect increases.As a result, the conversion efficiency of crystalline silicon solar cell improves.
Shown in Fig. 3 graphical representation supply to interelectrode electric power frequency with collide substrate surface
Relation [bright long matsuda etc. the, " supply frequency impact on GD non-crystalline silicon characteristic of number of ions
(Influence of Power-Source Frequency on the Properties of GD a-Si:
H) ", applied physics Japanese journal (Japanese Journal of Applied Physics),
Vol.23, No.8,1984 year August, L568-L569].As it is shown on figure 3, frequency be 10kHz～
The number of ions colliding substrate in the case of 500kHz is many, and is more than or equal to 1MHz's in frequency
In the case of to collide the number of ions of substrate few.
Therefore, the frequency by being fed to the alternating electromotive force between substrate base 12 and electrode 13 sets
For 10kHz～500kHz, be the situation more than or equal to 1MHz compared to frequency, can make in a large number from
Son collides substrate 100.As already explained, by making H ion etc. collide substrate 100, and
The surface of substrate 100 and the passivation effect of inside can be increased.It addition, for more really, preferably will hand over
The frequency of stream electric power is set to 50kHz～450kHz.
As described, according to film forming device 10, by the alternating current that alternating current power supply 14 is supplied
The frequency of power is set to 50kHz～450kHz, and the passivation effect of the surface of substrate 100 and inside increases.
It is, according to film forming device 10, the thin film that passivation effect is high can be formed.Thus, can improve
The conversion efficiency of such as solar cell.
Below, it is considered to following situation: utilize the film forming device 10 shown in Fig. 1 to form silicon metal
It it is the antireflection film of solar cell.It is, substrate 100 is crystalline silicon solar cell substrate, blunt
Changing film 110 is antireflection film.Now, in substrate 100, can use and be formed on P-type silicon substrate
Diffusion into the surface concentration is 1 × 1018～1 × 1022The substrate of n-type semiconductor layer, or can use at n
Forming diffusion into the surface concentration on type silicon substrate is 1 × 1018～1 × 1022The substrate of p type semiconductor layer
Deng.And, passivating film 110 for refractive index be 1.3～3.0, thickness be 50nm～about 150nm
Silicon nitride (SiN) film etc..
In order to form the passivating film 110 such as comprising SiN film on the substrate 100, unstrpped gas uses
Single silane (monosilane), ammonia (ammonia) etc., and as vector gas, use nitrogen (N),
Hydrogen (H), argon (Ar), helium (He) etc..
The width setup of groove 132 is 5mm～10mm.In the case of utilizing hollow cathode discharge, shape
The width becoming the groove on the surface of high-frequency electrode is usually about 1mm～4mm.Film forming device 10
In, by the width of enlarged slot 132, and plasma can be stably formed.But, if width
Excessive, then the state of plasma easily becomes unstable, thus the width of preferred groove 132 is less than
10mm.Although it addition, the diameter of the peristome of squit hole 131 also depends on is formed at electrode 13
The quantity of squit hole 131, but be generally speaking less than or equal to 1mm.
Generally, in the case of utilizing hollow cathode discharge, the pressure of reacting gas is for being more than or equal to
500Pa.But, in film forming device 10, in order to be stably formed plasma in chamber 11
Body, and be preferably set to comprising the unstrpped gas pressure with the reacting gas 120 of vector gas as little as
About 50Pa～100Pa.
And, plasma is excited in chamber 11, just realize the conversion of high solar cell
For efficiency (hereinafter referred to as " conversion efficiency ") this point, preferably substrate 100 is set as 250
DEG C～550 DEG C.As the relation that Fig. 4 represents substrate temperature and conversion efficiency, substrate temperature is 300
DEG C～when 450 DEG C, it is thus achieved that the high conversion efficiency of 15.6%～more than 16%.
In film forming device 10 shown in Fig. 1, utilize the heater 17 being built in substrate base 12,
Can at random set the temperature of substrate 100.As described, by the temperature of substrate 100 is set
It is 300 DEG C～450 DEG C, and obtains high conversion efficiency.Additionally, more preferably the temperature of substrate 100 is set
It it is 400 DEG C～450 DEG C.
Hereinafter, Fig. 5 is expressed as follows example: use respectively the film forming device 10 shown in Fig. 1 with than
The film forming device of relatively example, forms the passivating film 110 antireflection as crystalline silicon solar cell
Film.Herein, the frequency of the alternating electromotive force of film forming device 10 is 250kHz.In comparative example 1,
The frequency of alternating electromotive force is 250kHz, does not use hollow cathode electrode to use parallel-plate electrode
(parallel-plate electrode).In comparative example 2, use hollow cathode electrode, alternating current
The frequency of power is 13.56MHz.It addition, made crystalline silicon solar cell is at polycrystalline silicon substrate
The structure of the SiN film of upper formation thickness 80nm.
As it is shown in figure 5, with regard to the comparison that frequency is 250kHz of film forming device 10 with alternating electromotive force
For example 1, solar cell conversion efficiency is identical.But, the rate of film build of comparative example 1 is 28nm/
Minute, on the other hand, the rate of film build of the film forming device 10 employing hollow cathode electrode is 180
Nm/ minute, the film forming efficiency of film forming device 10 was the highest.
And, with regard to film forming device 10 with employ the comparative example 2 of hollow cathode electrode for, become
Film speed is equal.But, the frequency of alternating electromotive force is the solar cell of the comparative example 2 of 13.56MHz
Conversion efficiency is 16.3%, and on the other hand, the solar cell conversion efficiency of film forming device 10 is
16.5%, it is greater than comparative example 2.It is, passivation effect in the high comparative example 2 of the frequency of alternating electromotive force
The decline of fruit is big, thus conversion efficiency reduces.On the other hand, in film forming device 10, and compare
Example 2 is compared, and the decline of passivation effect is inhibited, thus obtains high conversion efficiency.
Therefore, in film forming device 10, obtain the high sun by supplying low-frequency ac electrode
Battery conversion efficiency, and by using hollow cathode electrode to realize high film forming efficiency.
As discussed above, in the film forming device 10 of embodiments of the present invention, use
Frequency is the alternating electromotive force of 50kHz～450kHz, and can realize make use of the one-tenth of hollow cathode discharge
Film.Result, it is possible to provide form the thin film that suppressed of decline of passivation effect and high thin of film forming efficiency
Membrane formation device 10.
The most as described, embodiment describe the present invention, it should be understood that become in the disclosure
Discussion and the accompanying drawing of the part held do not limit the present invention.According to the disclosure, for this area
For technical staff, various replacement embodiment, embodiment and application technology should be apparent from.
Fig. 1 illustrates following example: reacting gas 120 passes through the inside of electrode 13, and reacts
Gas 120 sprays in chamber 11 from the peristome of the squit hole 131 on the surface being formed at electrode 13.
But, it is not the feelings of shower plate (shower plate) type electrode as described at electrode 13
Under condition, it is possible to use the present invention.
Such as, as shown in Figure 6, it is possible to make reacting gas 120 not by the inside of electrode 13, and make
Reacting gas 120 directly imports from gas supply mechanism 15 in chamber 11.Thin film shown in Fig. 6
Being formed in device 10, surface forms the electrode 13 of groove 132 and also serves as hollow cathode electrode and play
Function.It is, in being formed at the groove 132 on surface of electrode 13, draw hollow cathode effect
The inclosure of generating, thus stably generate high-density plasma.As a result, unstrpped gas is by efficiently
Ground decompose, at a high speed, large area and the most on the substrate 100 formed passivating film 110.It addition, with figure
Film forming device 10 shown in 1 similarly, in the film forming device 10 shown in Fig. 6, groove
The layout of 132 may be used without various composition.It is, groove 132 both can be formed on clathrate ground, it is possible to
Striated ground is formed.
And, as it is shown in fig. 7, the present invention may also apply to there is multiple position being configured with substrate 100
The film forming device 10 put.In example shown in Fig. 7, substrate base 12 and electrode 13 form tool
There are the comb shape shape of the multiple toothed portions mutually extended towards above-below direction respectively, substrate base 12 along paper
With the toothed portion interdigital of the comb of electrode 13 configure.Substrate 100 is equipped on substrate base respectively
12 relative with electrode 13 to multiple toothed portions.
And, from gas supply mechanism 15 to the chamber of the Fig. 7 vertically configuring multiple substrate 100
Reacting gas 120 is imported in 11.Groove 132, electrode 13 is formed on the surface of the toothed portion of electrode 13
The function as hollow cathode electrode.In the example shown in Fig. 7, groove 132 through electrode 13
Toothed portion and formed.According to the film forming device 10 shown in Fig. 7, can be simultaneously at multiple substrates 100
Upper formation passivating film.
So, the present invention comprises the various embodiments etc. herein do not recorded certainly.Therefore, the present invention
Technical scope only specified by the specific item of invention of rational claim according to described explanation.
Industrial applicability
The film forming device of the present invention can be used for being formed the thin film that suppressed of decline of passivation effect
In purposes.
Claims (9)
1. a film forming device, forms passivating film, it is characterised in that including on substrate:
Chamber, is imported into the reacting gas of the unstrpped gas comprising described passivating film；
Substrate base, is configured in described chamber, and loads described substrate；
Electrode, is configured in described chamber, in described substrate base relative with described substrate to
Face forms groove；And
Alternating current power supply, makes more than or equal to 50kHz and the frequency less than or equal to 450kHz
Stopping for the cycle giving to fix, by the supply of described alternating electromotive force to described substrate of alternating electromotive force
Between base plate and described electrode, and the upper surface of described substrate excite comprise described unstrpped gas etc.
Gas ions,
Wherein, in the described groove of described electrode, produce hollow cathode discharge, simultaneously with described fixing
Cycle make the supply of described alternating electromotive force stop, in described chamber, make described plasma whereby
Stable.
Film forming device the most according to claim 1, it is characterised in that:
In the bottom of the described groove being formed at described electrode, it is multiple that the formation described reacting gas of confession passes through
The peristome of squit hole.
Film forming device the most according to claim 1, it is characterised in that:
The time that the supply of described alternating electromotive force stops is more than or equal to 25 microseconds and less than or equal to 50
Microsecond.
Film forming device the most according to claim 1, it is characterised in that:
The width of described groove is more than or equal to 5mm and less than or equal to 10mm.
Film forming device the most according to claim 1, it is characterised in that:
Also including heater, described heater, will when described plasma is excited
Described substrate is set greater than or equal to 300 DEG C and less than or equal to 450 DEG C.
Film forming device the most according to claim 1, it is characterised in that:
The pressure of the described reacting gas in described chamber be set greater than or equal to 50Pa and less than or
Equal to 100Pa.
Film forming device the most according to claim 1, it is characterised in that:
Described substrate is crystalline silicon solar cell substrate.
Film forming device the most according to claim 7, it is characterised in that:
The antireflection film that described passivating film is crystalline silicon solar cell being formed on described substrate.
Film forming device the most according to claim 1, it is characterised in that:
The film forming speed of the described passivating film being formed on described substrate is for divide more than or equal to 180nm/
Clock.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011113241 | 2011-05-20 | ||
| JP2011-113241 | 2011-05-20 | ||
| PCT/JP2011/071655 WO2012160718A1 (en) | 2011-05-20 | 2011-09-22 | Thin film forming device |
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| Publication Number | Publication Date |
|---|---|
| CN103534383A CN103534383A (en) | 2014-01-22 |
| CN103534383B true CN103534383B (en) | 2016-08-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201180069697.2A Expired - Fee Related CN103534383B (en) | 2011-05-20 | 2011-09-22 | Film forming device |
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|---|---|
| JP (1) | JPWO2012160718A1 (en) |
| KR (1) | KR101535582B1 (en) |
| CN (1) | CN103534383B (en) |
| WO (1) | WO2012160718A1 (en) |
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| TWI641292B (en) | 2008-08-04 | 2018-11-11 | Ａｇｃ北美平面玻璃公司 | Plasma source |
| JP6508746B2 (en) | 2014-12-05 | 2019-05-08 | エージーシー フラット グラス ノース アメリカ，インコーポレイテッドＡｇｃ Ｆｌａｔ Ｇｌａｓｓ Ｎｏｒｔｈ Ａｍｅｒｉｃａ，Ｉｎｃ． | Plasma source using macro particle reduction coating and method of using plasma source with macro particle reduction coating for thin film coating and surface modification |
| MX2017007356A (en) | 2014-12-05 | 2018-04-11 | Agc Flat Glass Europe S A | Hollow cathode plasma source. |
| CN107710386B (en) * | 2015-06-05 | 2021-12-21 | 应用材料公司 | Process chamber |
| JP6565502B2 (en) * | 2015-09-03 | 2019-08-28 | 株式会社島津製作所 | Film forming apparatus and film forming method |
| US9721765B2 (en) | 2015-11-16 | 2017-08-01 | Agc Flat Glass North America, Inc. | Plasma device driven by multiple-phase alternating or pulsed electrical current |
| US10573499B2 (en) | 2015-12-18 | 2020-02-25 | Agc Flat Glass North America, Inc. | Method of extracting and accelerating ions |
| CN109576669A (en) * | 2018-12-19 | 2019-04-05 | 北京建筑大学 | A kind of hollow cathode discharge system and the method for preparing DLC film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101874293A (en) * | 2008-02-26 | 2010-10-27 | 株式会社岛津制作所 | Method for plasma deposition and plasma CVD system |
| CN102002687A (en) * | 2009-09-02 | 2011-04-06 | 应用材料股份有限公司 | Gas mixing method realized by back diffusion in a PECVD system with showerhead |
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| JP2001093843A (en) * | 1999-09-27 | 2001-04-06 | Kanegafuchi Chem Ind Co Ltd | Plasma cvd apparatus and method for manufacturing silicon-based thin-film photoelectric converter |
| DE10326135B4 (en) * | 2002-06-12 | 2014-12-24 | Ulvac, Inc. | A discharge plasma processing system |
| JP3837539B2 (en) * | 2003-03-25 | 2006-10-25 | 独立行政法人産業技術総合研究所 | Plasma CVD equipment |
| JP5105898B2 (en) * | 2007-02-21 | 2012-12-26 | 株式会社アルバック | Silicon thin film deposition method |
| JP5018688B2 (en) * | 2008-08-08 | 2012-09-05 | 株式会社島津製作所 | Film forming apparatus and film forming method |
| JP5496568B2 (en) * | 2009-08-04 | 2014-05-21 | 東京エレクトロン株式会社 | Plasma processing apparatus and plasma processing method |
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2011
- 2011-09-22 WO PCT/JP2011/071655 patent/WO2012160718A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101874293A (en) * | 2008-02-26 | 2010-10-27 | 株式会社岛津制作所 | Method for plasma deposition and plasma CVD system |
| CN102002687A (en) * | 2009-09-02 | 2011-04-06 | 应用材料股份有限公司 | Gas mixing method realized by back diffusion in a PECVD system with showerhead |
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| JPWO2012160718A1 (en) | 2014-07-31 |
| KR20130135351A (en) | 2013-12-10 |
| CN103534383A (en) | 2014-01-22 |
| WO2012160718A1 (en) | 2012-11-29 |
| KR101535582B1 (en) | 2015-07-09 |
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